Curable compositions for optical materials, and their applications

Abstract

To provide an optical material curable composition with a high refractive index and good solubility. [Solution] A curable composition for optical materials comprising an unsaturated monomer represented by general formula (1). (In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R3 represents an optionally substituted aryl group, an optionally substituted heterocyclic group, or the following general formula (2). X1 represents a direct bond or a divalent linking group.) (In general formula (2), R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X2 represents a direct bond or a divalent linking group. R 11 and R 12 (Both are hydrogen atoms, or both represent bonds that form an aromatic ring or a heterocycle.)

Description

Technical Field

[0001] The present invention relates to a curable composition for optical materials and their uses.

Background Art

[0002] Conventionally, organic compounds (monomers, resins, additives) used in optical materials and the like have been required to have not only a high refractive index but also solubility from the viewpoints of processability and handling properties. In response to such problems, Patent Documents 1 to 3 disclose monomers containing a fluorene group as high refractive index materials. However, the solubility was not sufficient. On the other hand, Non-Patent Document 1 reports monomers and resins containing a diphenyl sulfide skeleton, but only limited basic physical properties such as infrared spectroscopy and thermal analysis have been confirmed, and various physical properties such as refractive index and solubility are completely unknown.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0004]

Non-Patent Document 1

[0006] As a result of diligent research, the inventors of this invention discovered that the above problem could be solved by incorporating an arylphenyl sulfide skeleton into a resin, leading to the present invention.

[0007] [1] A curable composition for optical materials comprising an unsaturated monomer represented by the following general formula (1). General formula (1) [ka] (In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R3 represents an optionally substituted aryl group, an optionally substituted heterocyclic group, or the general formula (2) below. X1 represents a direct bond or a divalent linking group.) General formula (2) [ka] (In general formula (2), R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X2 represents a direct bond or a divalent linking group. 11 and R 12 Both are hydrogen atoms, or both form an aromatic ring or a heterocycle. * represents a bond.

[0008] [2] The curable composition for optical materials according to [1], further comprising a photopolymerization initiator.

[0009] [3] A curable composition for optical materials according to [1] or [2], wherein X1 in general formula (1) is -C(=O)-.

[0010] [4] The curable composition for an optical material according to any one of [1] to [3], having a refractive index of 1.60 or more at 23°C and a wavelength of 594 nm.

[0011] [5] A film obtained by using the curable composition for an optical material according to any one of [1] to [4].

[0012] [6] An optical material obtained by using the curable composition for an optical material according to any one of [1] to [5].

Advantages of the Invention

[0013] According to the present invention described above, a curable composition for an optical material having both a high refractive index and high solubility can be provided.

[0014] As described above, the curable composition for an optical material of the present invention has properties such as transparency and a high refractive index. The use is not limited as long as it is a material that requires a high refractive index, but it can be suitably used for optical materials such as sealing materials, protective layers, optical fibers, optical films, optical lenses, and optical waveguides. In particular, it is useful as an optical lens material that requires high transparency and refractive index.

Embodiments for Carrying Out the Invention

[0015] <Regarding the curable composition of the present invention> In the present invention, "high refractive index" means that the refractive index at 23°C and a wavelength of 594 nm is 1.53 or more, preferably 1.57 or more, more preferably 1.62 or more, still more preferably 1.64 or more, and most preferably 1.67 or more. The curable composition for an optical material of the present invention contains an unsaturated monomer represented by the following general formula (1).

[0016] General formula (1)

Chemical formula

[0017] Examples of C1-C7 alkyl groups in R1 and R2 include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, isobutyl, isopentyl, cyclopentyl, and cyclohexyl groups.

[0018] From the viewpoint of ease of synthesis and various physical properties, R1 and R2 are preferably hydrogen atoms or methyl groups.

[0019] Examples of divalent substituents in X1 include *-C(=O)-, *-C(=O)-O-R6-, and *-C(=O)-R7-NH-C(=O)-. * represents a bond with a carbon atom. R6 and R7 represent alkylene groups having 1 to 7 carbon atoms, which may have substituents.

[0020] Examples of C1-C7 alkylene groups that may have substituents in R6 and R7 include methylene, ethylene, propylene, butylene, pentylene, hexylene, and heptylene groups, and may also have substituents such as hydroxyl, carboxyl, and alkyl groups having residues containing unsaturated double bonds.

[0021] Preferred structures for R6 include *-CH2-CH2(OH)-CH2-*, *-CH2-CH(CH2-OH)―*, and the following structures. * represents a bond. [ka] [ka] [ka] [ka]

[0022] The aryl group in R3 is a monocyclic or fused polycyclic aryl group having 6 to 24 carbon atoms. Specific examples include phenyl, 1-naphthyl, 2-naphthyl, 1-anthuryl, 9-anthuryl, 2-phenanthryl, 3-phenanthryl, 9-phenanthryl, 1-pyrenyl, 5-naphthacenyl, 1-indenyl, 2-azlenyl, 1-acenaphthyl, 2-fluorenyl, 9-fluorenyl, 3-perilenyl, o-tolyl, and m-tolyl groups. Examples of such groups include, but are not limited to, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, and m-azidophenyl group.

[0023] Heterocyclic groups in R3 include aromatic or aliphatic heterocyclic groups with 4 to 24 carbon atoms, containing nitrogen, oxygen, sulfur, and phosphorus atoms. Specific examples include 2-thienyl group, 2-benzothienyl group, naphtho[2,3-b]thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, clomenyl group, xanthenyl group, and phenoxanyl group. Thiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridadinyl group, indolidinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, prinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthylidinyl group, quinoxanillyl group, quinazolinyl group Synnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinel group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, flazanyl group, 3-phenixadinyl group, isochromanyl group, chromanyl group, pyrrolidinyl Examples of such groups include, but are not limited to, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, and 3-coumarinyl group.

[0024] Here, from the viewpoint of ease of synthesis and various physical properties, R3 is preferably a monocyclic or fused polycyclic aryl group having 6 to 14 carbon atoms, or an aromatic or aliphatic heterocyclic group having 4 to 8 carbon atoms, and more preferably a phenyl group.

[0025] In R3, the aryl group and heterocyclic group may have hydrogen atoms substituted with substituents.

[0026] Substituents include, for example, halogen groups such as fluorine, chlorine, bromine, and iodine atoms; alkoxy groups such as methoxy, ethoxy, and tert-butoxy groups; aryloxy groups such as phenoxy and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl groups; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy groups; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; and alkylamino groups such as methylamino and cyclohexylamino groups. Examples of such groups include dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, and piperidino group; arylamino groups such as phenylamino group and p-tolylamino group; alkyl groups such as methyl group, ethyl group, tert-butyl group, and dodecyl group; aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthuryl group, and phenanthryl group; heterocyclic groups such as furyl group and thienyl group; as well as hydroxyl group, carboxyl group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, and triphenylphenacylphosphoniumyl group. These can be selected within the scope that does not impair the spirit of the present invention.

[0027] The structure represented by general formula (2) in R3 is preferred because it exhibits higher curability and improves the solvent resistance of the cured product. The alkyl groups having 1 to 7 carbon atoms in R4 and R5 in general formula (2) are the same as those shown for R1 and R2.

[0028] The divalent substituents of X2 in general formula (2) are the same as those shown for X1.

[0029] The structure of general formula (1) can be described as follows: [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0030] The curable composition for optical materials of the present invention can achieve a high refractive index by containing an unsaturated monomer represented by general formula (1), and more specifically, can achieve a cured product with a refractive index of 1.60 or higher at 23°C and a wavelength of 594 nm. The content of the unsaturated monomer represented by general formula (1) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and may also be 90% by mass or more, based on the total solid content of the curable composition for optical materials. Within the above range, the refractive index is improved. Furthermore, the present invention may be used in combination with other monomers that have a high refractive index or other monomers that have high solubility, as long as the effects of the present invention are not impaired.

[0031] As an example of a preferred composition for the curable composition for optical materials, a form is provided in which the total solid content of the curable composition for optical materials contains 50 to 95% by mass of an unsaturated monomer represented by general formula (1), 0 to 45% by mass of other curable monomers, and 0.05 to 5% by mass of a photopolymerization initiator. With the above composition, the refractive index and solubility are good, and furthermore, solvent resistance is improved.

[0032] <Other polymerizable monomers> The curable composition for optical materials of the present invention can use polymerizable monomers other than the unsaturated monomer represented by general formula (1), and can be used as a curable composition by adding polymerizable monomers and / or polymerization initiators. Other polymerizable monomers can be used as curing agents, and the cured product will have improved properties such as solvent resistance. The polymerizable monomers of the present invention include monomers or oligomers that harden upon exposure to ultraviolet light or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

[0033] Examples of monomers and oligomers that harden to produce transparent resins by ultraviolet light or heat include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri( Meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated melamine (meth)acrylic acid esters, epoxy(meth)acrylate, urethane acrylate, and other various acrylic acid esters and methacrylic acid esters. Examples include, but are not limited to, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0034] These commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120 from Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-32 from Toagosei Co., Ltd. 1. Suitable products include M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 from Osaka Organic Chemicals Co., Ltd., and NK Ester A-9300 from Shin Nakamura Chemical Co., Ltd.

[0035] (Polymerizable compounds containing acidic groups) The curable composition for optical materials in the present invention may contain polymerizable compounds having acidic groups. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0036] Examples of polymerizable compounds having acidic groups include poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohols and (meth)acrylic acid, esterified with dicarboxylic acids; esterified polycarboxylic acids and monohydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, and monoesterified poly(meth)acrylates containing free carboxyl groups of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and propane-1,2,3-tricarboxylic acid (tricarvalic acid). Examples include oligoesters containing free carboxyl groups formed by the interaction of tricarboxylic acids such as butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid with monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, but the effects of the present invention are not limited to these.

[0037] Suitable commercially available products include Viscoat #2500P from Osaka Organic Co., Ltd., and Aronics M-5300, M-5400, M-5700, M-510, M-520, etc. from Toagosei Co., Ltd.

[0038] (Polymerizable compound containing urethane bonds) The curable composition for optical materials in the present invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. Examples include polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl group-containing (meth)acrylate.

[0039] Examples of (meth)acrylates containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

[0040] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0041] Suitable commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 from Kyoeisha Chemical Co., Ltd., UA-160TM from Shin Nakamura Chemical Industry Co., Ltd., and UV-4108F and UV-4117F from Osaka Organic Chemical Industry Co., Ltd.

[0042] Other polymerizable monomers can be used individually or mixed in any ratio of two or more as needed.

[0043] When using other polymerizable monomers, if they are bifunctional or more, photocurability improves, and solvent resistance also tends to improve.

[0044] The amount of other polymerizable monomers is preferably 1 to 50% by mass, and more preferably 2 to 40% by mass, based on the total nonvolatile content of the curable composition (100 parts by mass).

[0045] <Photopolymerization initiator> The curable composition for optical materials of the present invention can be cured by ultraviolet irradiation by containing a photopolymerization initiator. The amount of photopolymerization initiator used is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass, based on the total amount of the curable composition.

[0046] Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl- Acetophenone compounds such as 2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butyl) Benzophenone compounds such as peroxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(tri(methoxyphenyl)-s-triazine, 2-(p-tolyl)-4,6-bis(tri(tri(methoxyphenyl)-s-tri(methoxyphenyl)-s-triazine); 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(). Triazine compounds such as chloromethyl-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxynaphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthylenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds are used. In particular, oxime ester compounds are highly sensitive and exhibit photocurability even in small amounts, making them preferable for forming fine patterns.

[0047] These photopolymerization initiators can be used individually or, if necessary, as a mixture of two or more in any ratio.

[0048] (others) Other materials may be used in the curable composition for optical materials of the present invention as appropriate. Examples of other materials include sensitizers and leveling agents.

[0049] Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, and the like.

[0050] As a leveling agent, those having both hydrophobic and hydrophilic groups in their molecule are particularly preferred. These are a type of surfactant, and while they have hydrophilic groups, they have low solubility in water and, when added to a composition, have low surface tension reduction ability. Furthermore, those that have good wettability to glass plates despite low surface tension reduction ability are useful, and those that can sufficiently suppress electrostatic charge at an amount that does not cause defects in the coating film due to foaming are preferably used. Dimethylpolysiloxane having polyalkylene oxide units is preferably used as a leveling agent having such desirable properties. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

[0051] Furthermore, the bonding configuration of the polyalkylene oxide units to dimethylpolysiloxane may be any of the following: a pendant type in which the polyalkylene oxide units are bonded to the repeating units of dimethylpolysiloxane; a terminally modified type in which they are bonded to the ends of dimethylpolysiloxane; or a linear block copolymer type in which they are alternately bonded to dimethylpolysiloxane in repeating units. Dimethylpolysiloxane having polyalkylene oxide units is commercially available from Toray Dow Corning Co., Ltd., and examples include, but is not limited to, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

[0052] (film) Films obtained by curing the curable composition for optical materials of the present invention by solvent evaporation, exposure (photocuring), or heating (thermocuring) are also subject to the present invention. Examples of light rays used for exposure include ultraviolet rays, electron beams, and X-rays. Light sources for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. Furthermore, post-baking may be performed after exposure to stabilize the physical properties of the cured material. While there are no particular limitations on the post-baking method, it is usually performed using a hot plate, oven, etc., at a temperature of 50-260°C for 1-120 minutes. The heating conditions for thermosetting are not particularly limited, but are usually appropriately selected from the range of 50 to 300°C and 1 to 120 minutes. The heating means are also not particularly limited, but examples include hot plates and ovens.

[0053] A film formed using a composition containing the above-described curable composition for optical materials of the present invention has a high refractive index and can be suitably used as an optical material as a high refractive index material. Optical materials are components designed to transmit light; for example, they are components used in optical instruments that allow light to pass through. Because optical materials often require a specific refractive index, high refractive index films are used in various components of optical instruments. Optical materials are particularly suitable for optical lenses and optical waveguides, and can also be used as anti-reflective films, light-scattering films, prism sheets, diffraction gratings, and decorative films for matte or gloss finishes.

[0054] Optical lenses refer to lenses used to focus light, and examples include eyeglass lenses, optical instrument lenses, optoelectronic lenses, laser lenses, pickup lenses, automotive camera lenses, mobile phone camera lenses, digital camera lenses, OHP lenses, and microlenses. These lenses are particularly required to have a high refractive index and are suitable for use with the curable composition of the present invention. An optical waveguide refers to a waveguide used to propagate light, and its shape is not limited to sheets, plates, etc. Applications include, for example, cables used for optical communication in computers and sensor devices, optical interconnects used for optical communication within devices, and materials used on the optical path when infrared sensors sense infrared light.

[0055] Furthermore, the curable composition for optical materials can be molded into any shape, such as a dome or a sheet. For example, the composition can be molded as follows: The curable composition of the present invention, containing a photopolymerization initiator and a photopolymerizable monomer, is potted onto a transparent substrate such as glass. A desired molding die is then pressed onto the potted composition, filling it into the mold. The composition can then be cured by light irradiation. After that, the mold is removed to obtain a cured product of the composition integrated on the transparent substrate. Alternatively, the composition can be filled into a light-transmitting transparent mold and photocured. A hybrid lens, for example, can be manufactured using this method. Furthermore, the curable composition of the present invention can also be cured on its own within a molding die to form optical components such as optical lenses. These methods are called optical nanoimprinting, but a method called thermal nanoimprinting, in which the composition is filled into a molding die and then cured at high temperatures, can also be used. Furthermore, the material can be molded as a microlens. One known method for manufacturing microlenses is the etch-back method. A resist pattern is formed on a coating film of the curable composition of the present invention, and this resist pattern is reflowed by heat treatment to form a lens pattern. Using the lens pattern formed by reflowing this resist pattern as an etching mask, the underlying coating film is etched back, and the lens pattern shape is transferred to the coating film to produce a microlens. Another method for manufacturing microlenses involves exposing and developing the curable composition of the present invention, which contains a photopolymerization initiator and an alkali-soluble resin, to form a resist pattern, and then reflowing it by heat treatment to produce a microlens. In particular, when deploying microlenses on organic EL elements, curing at around 100°C is necessary. This is because organic EL elements cannot withstand high temperatures. In this case, curing with (meth)acryloyl groups is effective. Examples of crosslinkable functional group combinations that cure sufficiently at 100°C include hydroxyl groups and isocyanate groups, and hydroxyl groups and acid anhydride groups. However, these reactions proceed even at room temperature, which tends to worsen storage stability. In contrast, (meth)acryloyl groups do not significantly worsen storage stability and have the characteristic of curing at around 100°C. In particular, adding a photopolymerization initiator and combining it with an exposure process enhances curability and is very effective. Examples of applications where microlenses are deployed on organic EL elements include micro-OLED displays and OLED displays. Furthermore, when forming an optical waveguide, a resist pattern can be formed by exposing and developing the curable composition of the present invention, which contains a photopolymerization initiator and an alkali-soluble resin, and then exposing and developing another dispersion composition containing a photopolymerization initiator and an alkali-soluble resin, but with a different refractive index, to form adjacent resist patterns, thereby forming a core and a cladding and creating an optical waveguide. [Examples]

[0056] The present invention will be described in more detail below, but the present invention is not limited to these embodiments without departing from the technical concept of the present invention. Hereinafter, "parts by mass" will be written as "parts" and "% by mass" will be written as "%".

[0057] <Production of unsaturated monomers represented by general formula (1)> (Manufacturing of monomer (A1)) In a 100cc flask, 10 mmol of 2-aminophenylphenyl sulfide was mixed with 15 mmol of methacrylic anhydride and 20 g of N,N-dimethylformamide, followed by 0.01 mmol of methylhydroquinone. The mixture was reacted at 80°C for 5 hours while bubbling air through the flask. Thin-layer chromatography confirmed that the starting materials had disappeared. The reaction solution was then added to a 500cc flask containing 200 g of water, and a white precipitate appeared. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered material was then vacuum-dried at 80°C for 10 hours to obtain monomer (A1) 8.1 mmol.

[0058] (Manufacturing of monomer (A2)) In the preparation of monomer (A1), the procedure was the same as that for monomer (A1), except that 2-aminophenylphenyl sulfide was replaced with 3-aminophenylphenyl sulfide, and 8.0 mmol of monomer (A2) was obtained.

[0059] (Manufacturing of monomer (A3)) In the preparation of monomer (A1), the procedure was the same as that for monomer (A1), except that methacrylic anhydride was replaced with acrylic anhydride, and 7.5 mmol of monomer (A3) was obtained.

[0060] (Manufacturing of monomer (A4)) In the preparation of monomer (A2), the procedure was the same as that for monomer (A2), except that methacrylic anhydride was replaced with acrylic anhydride, and 7.5 mmol of monomer (A4) was obtained.

[0061] (Manufacturing of monomer (A5)) In the preparation of monomer (A1), the procedure was the same as that for monomer (A1), except that 2-aminophenylphenyl sulfide was replaced with 4-aminophenylphenyl sulfide, and monomer (A2) 8.2 mmol was obtained.

[0062] (Manufacturing of monomer (A6)) In the preparation of monomer (A5), the procedure was the same as that for monomer (A5), except that methacrylic anhydride was replaced with acrylic anhydride, and 8.1 mmol of monomer (A2) was obtained.

[0063] (Manufacturing of monomer (A7)) In a 100cc flask, 10 mmol of bis(4-aminophenyl) sulfide was mixed with 25 mmol of methacrylic anhydride and 20 g of N,N-dimethylformamide, followed by 0.01 mmol of methylhydroquinone. The mixture was reacted at 80°C for 5 hours while bubbling air through the flask. Thin-layer chromatography confirmed that the starting materials had disappeared and the target product had been formed. The reaction mixture was then added to a 500cc flask containing 200 g of water, and a white precipitate appeared. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered material was then vacuum-dried at 80°C for 10 hours to obtain monomer (A7) 7.0 mmol.

[0064] (Manufacturing of monomer (A8)) In the preparation of monomer (A7), the procedure was the same as that for monomer (A7), except that bis(4-aminophenyl) sulfide was replaced with bis(2-aminophenyl) sulfide, and 7.2 mmol of monomer (A8) was obtained.

[0065] (Manufacturing of monomer (A9)) In the preparation of monomer (A7), the procedure was the same as that for monomer (A7), except that bis(4-aminophenyl) sulfide was replaced with bis(3-aminophenyl) sulfide, and monomer (A9) 7.2 mmol was obtained.

[0066] (Manufacturing of monomer (A10)) In a 100cc flask, 10 mmol of 2-aminophenylphenyl sulfide was mixed with 15 mmol of glycidyl methacrylate and 20 g of N,N-dimethylformamide, followed by 0.01 mmol of methylhydroquinone. The mixture was reacted at 100°C for 5 hours while bubbling air through the flask. After confirming the disappearance of the starting materials by thin-layer chromatography, the reaction solution was added to a 500cc flask containing 200 g of water, and a white precipitate appeared. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered substance was then vacuum-dried at 80°C for 10 hours to obtain 7.4 mmol of monomer (A10).

[0067] (Manufacturing of monomer (A11)) In a 100cc flask, 10 mmol of monomer (A10) was mixed with 1 mmol of methacrylic anhydride and 20 g of N,N-dimethylformamide, followed by 0.01 mmol of methylhydroquinone. The mixture was reacted at 80°C for 5 hours while bubbling air through the flask. After confirming the disappearance of the starting materials by thin-layer chromatography, the reaction solution was added to a 500cc flask containing 200 g of water, and a white precipitate appeared. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered substance was then vacuum-dried at 80°C for 10 hours to obtain 7.9 mmol of monomer (A11).

[0068] (Manufacturing of monomer (A12)) In the preparation of monomer (A11), the procedure was the same as that for monomer (A11), except that methacrylic anhydride was replaced with acrylic anhydride, and 7.8 mmol of monomer (A12) was obtained.

[0069] (Manufacturing of monomer (A13)) In a 100cc flask, 10 mmol of monomer (A10) was mixed with 15 mmol of Karenz MOI (2-isocyanatoethyl methacrylate, manufactured by Resonaq) and 20 g of N,N-dimethylformamide. Further, 0.01 mmol of methylhydroquinone was added, and the mixture was reacted at 80°C for 5 hours while bubbling air through the mixture. Thin-layer chromatography confirmed the disappearance of the starting materials. The reaction solution was then added to a 500cc flask containing 200 g of water, resulting in the appearance of a white precipitate. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered material was then vacuum-dried at 80°C for 10 hours to obtain 8.2 mmol of monomer (A13).

[0070] (Manufacturing of monomer (A14)) In the preparation of monomer (A13), the procedure was the same as that for monomer (A13), except that the kallenz MOI was replaced with kallenz AOI (2-isocyanatoethyl acrylate, manufactured by Resonaq), and 8.0 mmol of monomer (A14) was obtained.

[0071] (Manufacturing of monomer (A15)) In a 100cc flask, 10 mmol of bis(2-aminophenyl) sulfide was mixed with 25 mmol of glycidyl methacrylate and 20 g of N,N-dimethylformamide, followed by 0.01 mmol of methylhydroquinone. The mixture was reacted at 100°C for 5 hours while bubbling air through the flask. Thin-layer chromatography confirmed that the starting materials had disappeared and the target product had been formed. The reaction mixture was then added to a 500cc flask containing 200 g of water, and a white precipitate appeared. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered substance was then vacuum-dried at 80°C for 10 hours to obtain 7.0 mmol of monomer (A15).

[0072] (Manufacturing of monomer (A16)) In a 100cc flask, 10 mmol of monomer (A15) was mixed with 25 mmol of acrylic anhydride and 20 g of N,N-dimethylformamide, followed by 0.01 mmol of methylhydroquinone. The mixture was reacted at 80°C for 5 hours while bubbling air through the flask. Thin-layer chromatography confirmed that the starting materials had disappeared and the target product had been formed. The reaction mixture was then added to a 500cc flask containing 200 g of water, and a white precipitate appeared. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered material was then vacuum-dried at 80°C for 10 hours to obtain 8.1 mmol of monomer (A16).

[0073] (Manufacturing of monomer (A17)) In the preparation of monomer (A16), the procedure was the same as that for monomer (A17), except that acrylic anhydride was replaced with methacrylic anhydride, and 8.0 mmol of monomer (A17) was obtained.

[0074] (Manufacturing of monomer (A18)) In a 100cc flask, 10ml of bis(2-aminophenyl) sulfide was mixed with 10ml of acrylic anhydride and 20g of N,N-dimethylformamide, followed by 0.01ml of methylhydroquinone. The mixture was reacted at 80°C for 5 hours while bubbling air. Thin-layer chromatography confirmed that the starting materials had disappeared and the target product had formed. Next, 15ml of glycidyl methacrylate was added, and the mixture was reacted at 100°C for 5 hours while bubbling air. Thin-layer chromatography confirmed that the starting materials had disappeared and the target product had formed. Next, 10ml of acrylic anhydride was added, and the mixture was reacted at 100°C for 5 hours. Thin-layer chromatography confirmed that the starting materials had disappeared and the target product had formed. When the reaction mixture was added to a 500cc flask containing 200g of water, a white precipitate appeared. This was subjected to suction filtration, and then suction filtration was continued while sprinkling a total of 400g of water. The filtered substance was then vacuum-dried at 80°C for 10 hours to obtain monomer (A18) 8.1 mmol.

[0075] (Manufacturing of monomer (A19)) In a 100cc flask, 10 mmol of bis(2-aminophenyl) sulfide was mixed with 25 mmol of Karenz MOI (2-isocyanatoethyl methacrylate, manufactured by Resonaq) and 20 g of N,N-dimethylformamide. 0.01 mmol of methylhydroquinone was then added, and the mixture was reacted at 80°C for 5 hours while bubbling air through the mixture. Thin-layer chromatography confirmed the disappearance of the starting materials and the formation of the target product. The reaction solution was then added to a 500cc flask containing 200 g of water, resulting in the appearance of a white precipitate. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered material was then vacuum-dried at 80°C for 10 hours to obtain monomer (A19) 7.8 mmol.

[0076] (Manufacturing of monomer (A20)) In the preparation of monomer (A19), the procedure was the same as that for monomer (A19), except that the kallenz MOI was replaced with kallenz AOI (2-isocyanatoethyl acrylate, manufactured by Resonaq), and 8.0 mmol of monomer (A20) was obtained.

[0077] (Manufacturing of monomer (A21)) In the preparation of monomer (A19), the procedure was the same as that for monomer (A19), except that bis(2-aminophenyl) sulfide was replaced with 2-aminophenylphenyl sulfide, and 8.0 mmol of monomer (A21) was obtained.

[0078] (Manufacturing of monomer (A22)) In the preparation of monomer (A20), the procedure was the same as that for monomer (A20), except that bis(2-aminophenyl) sulfide was replaced with 2-aminophenylphenyl sulfide, and 8.1 mmol of monomer (A22) was obtained.

[0079] (Manufacturing of monomer (A23)) The same procedure as for the preparation of monomer (A1) was followed, except that 2-aminophenylphenyl sulfide was replaced with 2-(2-aminophenylthio)naphthalene, to obtain monomer (A23) 8.2 mmol.

[0080] (Manufacturing of monomer (A24)) The same procedure as for the preparation of monomer (A1) was followed, except that 2-aminophenylphenyl sulfide was replaced with 1-(2-aminophenylthio)naphthalene, to obtain monomer (A24) 8.1 mmol.

[0081] (Manufacturing of monomer (A25)) The same procedure as for the preparation of monomer (A1) was followed, except that 2-aminophenylphenyl sulfide was replaced with 2-(2-aminophenylthio)naphthalene, to obtain monomer (A25) 8.2 mmol.

[0082] (Manufacturing of monomer (A26)) In a 100cc flask, 10 mmol of (2-aminophenylthio)-3-aminonaphthalene was mixed with 25 mmol of methacrylic anhydride and 20 g of N,N-dimethylformamide, followed by 0.01 mmol of methylhydroquinone. The mixture was reacted at 80°C for 5 hours while bubbling air through the flask. Thin-layer chromatography confirmed that the starting materials had disappeared and the target product had been formed. The reaction mixture was then added to a 500cc flask containing 200 g of water, and a white precipitate appeared. This precipitate was filtered by suction, and suction filtration was continued while sprinkling a total of 400 g of water. The filtered material was then vacuum-dried at 80°C for 10 hours to obtain monomer (A26) 8.0 mmol.

[0083] (Manufacturing of monomer (A27)) In the preparation of monomer (A1), the procedure was the same as that for monomer (A1), except that 2-aminophenylphenyl sulfide was replaced with 1-(2-aminophenylthio)anthracene, and monomer (A27) 8.0 mmol was obtained.

[0084] (Manufacturing of monomer (A28)) The same procedure as for the preparation of monomer (A1) was followed, except that 2-aminophenylphenyl sulfide was replaced with 2-(2-aminophenylthio)furan, to obtain monomer (A28) 7.8 mmol.

[0085] (Manufacturing of monomer (A29)) The same procedure as for the preparation of monomer (A1) was followed, except that 2-aminophenylphenyl sulfide was replaced with 1-(2-aminophenylthio)pyrrole, to obtain monomer (A29) 7.8 mmol.

[0086] (Manufacturing of monomer (A30)) The same procedure as for the preparation of monomer (A1) was followed, except that 2-aminophenylphenyl sulfide was replaced with 1-(2-aminophenylthio)thiophene, to obtain monomer (A30) 7.8 mmol.

[0087] (Manufacturing of monomer (A31)) In the preparation of monomer (A1), the procedure was the same as that for monomer (A1), except that 2-aminophenylphenyl sulfide was replaced with 1-(2-aminophenylthio)pyridine, and monomer (A31) 7.9 mmol was obtained.

[0088] (Manufacturing of monomer (AA1)) The following compound described in Synthesis Example 6 of Japanese Patent Publication No. 2012-082386 was synthesized with reference to the publication. Monomer (AA1) [ka]

[0089] (Manufacturing of monomer (AA2)) The following compound described in Example 1 of Japanese Patent Publication No. 2020-70433 was synthesized with reference to the publication. Monomer (AA2) [ka]

[0090] <Evaluation of monomer solubility> The solubility of monomers (A1) to (A31) and (AA1) to (AA2) in cyclohexanone at 25°C was evaluated. The monomers were added to 100% by mass of cyclohexanone, stirred, and dissolved. The maximum mass percentage at which no turbidity or precipitation occurred was evaluated according to the following criteria. ◎:35% by mass or more 〇: 15% by mass or more ×: Less than 15% by mass

[0091] [Table 1]

[0092] <Preparation and evaluation of curable compositions for optical materials>

[0093] (Example 1) (Manufacturing of curable composition (B1)) As shown below, a photopolymerization initiator and a solvent were added to monomer (A1) and stirred and mixed until homogeneous to prepare a curable composition (B1).

[0094] [composition] Monomer (A1): 19.8 parts Photopolymerization initiator (BASF "Irgacure OXE02"): 0.2 parts Cyclohexanone: 80.0 parts

[0095] (Examples 2-31, Comparative Examples 1-4) (Manufacture of curable compositions (B2) to (B31), (BB1) to (BB4)) Curable compositions (B2) to (B31) and (BB1) to (BB4) were prepared in the same manner as curable composition (B1), except that the monomers were changed as shown in Table 2. The materials listed in the table are shown below. • Arronix M-402: Manufactured by Toagosei Co., Ltd., contains dipentaerythritol penta and hexaacrylate.

[0096] (Preparation of films for evaluation of curable compositions) Curable compositions (B1) to (B31) and (BB1) to (BB4) were applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, and then dried at 70°C for 20 minutes. After the substrate was cooled to room temperature, it was subjected to a pressure of 500 mJ / cm using an ultra-high pressure mercury lamp. 2 A substrate with a film thickness of 1.0 μm was obtained by exposing it to ultraviolet light.

[0097] (Measurement of refractive index) The obtained substrates were evaluated using the "Prism Coupler Model 2010" manufactured by Metricon, with the refractive index at 23°C and 594 nm determined, according to the following criteria. ◎: 1.63 or higher ○: 1.60 or higher and less than 1.63 △: 1.55 or higher and less than 1.60 ×: Less than 1.55

[0098] [Table 2]

[0099] (Example 32) (Manufacturing of curable composition (C1)) A mixture of the following composition was stirred and mixed until uniform to prepare a curable composition (C1).

[0100] [composition] Monomer (A1): 16.0 parts Photopolymerizable monomer (Aronix M-402, manufactured by Toagosei Co., Ltd.): 3.8 parts Photopolymerization initiator (BASF "Irgacure OXE02"): 0.2 parts Cyclohexanone: 80.0 parts

[0101] (Examples 32-62, Comparative Examples 5-9) (Manufacturing of curable compositions (C2) to (C31), (CC1) to (CC5)) Curable compositions (C2) to (C31) and (CC1) to (CC5) were prepared in the same manner as curable composition (C1), except that the monomers were changed as shown in Table 3.

[0102] (Preparation of films for evaluation of curable compositions) The curable compositions (C1) to (C31) and (CC1) to (CC5) were applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, and then dried at 70°C for 20 minutes. After the substrate was cooled to room temperature, it was subjected to a pressure of 500 mJ / cm using an ultra-high pressure mercury lamp. 2 A substrate with a film thickness of 1.0 μm was obtained by exposing it to ultraviolet light.

[0103] (Measurement of refractive index) The obtained substrates were evaluated using the "Prism Coupler Model 2010" manufactured by Metricon, with the refractive index at 23°C and 594 nm determined and assessed according to the following criteria. ◎: 1.63 or higher ○: 1.60 or higher and less than 1.63 △: 1.55 or higher and less than 1.60 ×: Less than 1.55

[0104] (Measurement of solvent resistance) The obtained substrates were immersed in cyclohexanone for 3 minutes, dried at 70°C for 5 minutes after immersion, and the rate of change in film thickness before and after immersion was measured and evaluated according to the following criteria. ◎: Change rate less than 3% ○: Change rate of 3% or more but less than 10% △: Change rate between 10% and less than 30% ×: Change rate of 30% or more

[0105] [Table 3] These results are shown in Table 3. According to the present invention, a curable composition with a high refractive index and high solubility can be obtained. Furthermore, a curable composition with good solvent resistance can be obtained.

Claims

1. A curable composition for optical materials comprising an unsaturated monomer represented by the following general formula (1). General formula (1) 【Chemistry 1】 (In general formula (1), R １ and R ２ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. ３ X represents an optionally substituted aryl group, an optionally substituted heterocyclic group, or the following general formula (2). １ (This represents a direct bond or a divalent linking group.) General formula (2) 【Chemistry 2】 (In general formula (2), R ４ and R ５ each independently represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X ２ represents a direct bond or a divalent linking group. R １１ and R １２ both represent a hydrogen atom or a bond that forms an aromatic ring or a heterocyclic ring. * represents a bond.)

2. The curable composition for optical materials according to claim 1, further comprising a photopolymerization initiator.

3. X in general formula (1) １ A curable composition for optical materials according to claim 1 or 2, wherein is -C(=O)-.

4. A curable composition for optical materials according to claim 1 or 2, wherein the refractive index at 23°C and a wavelength of 594 nm is 1.60 or higher.

5. A film made using the curable composition for optical materials according to claim 1 or 2.

6. An optical material comprising a curable composition for optical materials according to claim 1 or 2.

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